Process for breaking petroleum emulsions



Patented Mar. 28, 1944 PROCESS FOR G PETROLEUM EMULSIONS Melvin DeGroote,

Ullimt o and Bernhard Keiser, Webster Groves, Mo asslgnors to PetroliteCorporation, Ltd Wilmingio poration of Delaware mnelqacor- No Drawing.Application December :1, 1941, Serial No. mass Claims. (Cl. 252-341)This invention relates to the treatment of emulsions of mineral oil andwater, such as petroleum emulsions, for the purpose of separating theoil from the water.

The main object of our invention is to provide a novel process forresolving petroleum emulsions of the water-in-oil type that are commonlyreferred to as "cut oil, roily oil, emulsified oil, etc., and whichcomprise fine droplets of naturally-occurring waters or brines dispersedin a more or less permanent state throughout the oil which constitutesthe continuous phase of the emulsion.

Another object: of our invention is to provide I an economical and rapidprocess for separating emulsions which have been prepared undercontrolled conditions from mineral oil, such as crude oil and relativelysoft waters or weak brines. Controlled emulsiflcation and subsequentdemulsiilcation under the conditions just mentioned is of significantvalue in removing impurities, particularly inorganic salts from pipelineoil.

The demulsifier or demulsifying agent employed in the present processconsists of a sub-resinous or -resinous product obtained by reactionbetween a polybasic acid or its equivalent, such as the anhydride, and ahydroxyiated ester diamlde of the kind in which the amido acyl radicalis characterized by being derived from a polybasic carboxy acid havingnot over 10 carbon atoms. and preferably 8 carbon atoms, or less. Theacyloxy radical or radicals are characterized by being derived from amonocarboxy detergentiorming acid having at least 8- and not more than32 carbon atoms.

It is well known that certain monocarboxy organic acids containing eightcarbon atoms or more, and not more than 32 carbon atoms, arecharacterized by the fact that they combine with alkalies to producesoap or soap-like materials. These detergent-forming acids include fattyacids, resin acids, petroleum acids, etc. For the sake of convenience,these acids will be indicated by the formula R'COOH. Certain derivativesof detergent-forming acids react with alkali to produce soap orsoap-like materials, and are the ob vious equivalent of the unchanged orunmodified detergent-forming acids; for instance, instead of fattyacids, one might employ the chlorinated fatty acids. Instead of theresin acids, one might employ the hydrogenated resin acids. Instead ofnaphthenic acids, one might employ brominated naphthenic acids, etc.

The fatty acidsare of the type commonly re- (erred to as higher fattyacids; and of course, this Such unsaturated fatty II. 8. Patent No.

is also true in regard to derivatives of the kind indicated, insofarthat such derivatives are obtained from higher fatty acids. Thepetroleum acids include notonly naturally-occurring naphthenic acids,but also acids obtained by the oxidation of wax, paraffin, etc. Suchacids may have as many as 32 carbon atoms. For instance, see 2,242,837,dated May 20, 1941, to Shields.

Although any of the high acids can be converted by conventionalprocedure, into new hydroxylated ester diamides of the kind described,it is our preference to employ hydroxylated ester diamides derived fromhigher fatty acids, rather than petroleum acids, rosin acids, and thelike. We have found that by far the most effective demulsifying agentsare obtained from unsaturated fatty acids having 18 carbon atoms. acidsinclude the higher fatty acids, such as oleic acid, ricinoleic acid,linoleic acid, linolenic acid. etc. One may employ mixed fatty acids,as, for example, the fatty acids obtained by the hydrolysis ofcottonseed oil, soyabean oil, corn oil, etc. Our preferred demulsifieris obtained from unsaturated fatty acids, and

more especially, unsaturated fatty acids having a hydroxyl radical, orunsaturated fatty acids which have been subjected to oxidation oroxyalkylation, such as oxyethylation.

The hydroxylated ester diamides of the kind herein described, may beobtained in any conventional manner. They are usually obtained from theacids themselves, or preferably, the anhydrides. If desired, however,functional equivalents, such as the acyl chlorides, esters, or otherderivatives, may be employed. In many instances the esters prove to bethe most suitable raw material, due to their case of reaction. Thediamlde of a low molal polycarboxy acid, particularly a dibasic acid,may be'treated with an oxyalkylating agent. such as ethylene oxide,propyleneoxide, butylene oxide, or the like, so as to produce a compoundof the following types:

. o aikylene.0H

alkylene. O H

ulkylenaOH Actually the alkylene radical might represent an equivalentdivalent radical in which the carbon atom chain is interrupted at leastonce by oxygen. as in C:H4OCzH4-.

molal monocarboxy "available, or can be prepared readily.

A procedure that is frequently more readily adaptable is simply thereaction between a low molal acid, such as oxalic acid, phthalic acid,

maleic-acid, or the low molal esters thereof, for

instance, the dimethyl ester, diethyl ester, or the like, anddiethanolamine, dipropanolamine, or the like. .For the sake of brevity,reference hereafter will be made to maleic acid esters and phthalic acidesters of monoethanolarnine, diethanolamine, or the like, although othersuitable reactants, have already been described. The method ofmanufacturing such ester diamides is simply a variant of the generalmethod of manufacturing esteramides, and is so well known that nofurther description is required. For convenience, reference is made toU. S. Patent No. 2,238,902, dated April 22, 1941, to Katzman and Harris.Note specifically that this patent teaches a procedure involvingconventional steps, such as reaction of monoethanolamine with a diethylester of oxalic acid, with subsequent acylation of the diamide withlauric acid. Similar derivatives derived from dimethyl phthalate and thelike, are described.

Actually, in the manufacture of demulsiflers we have followedsubstantially the same procedure as described in the above mentionedKatzman and Harris patent, as far as producing an intermediate isconcerned; but we have found that the most desirable compounds areobtained from unsaturated fatty acids, as previously described. Thus, wehave substituted oleic acid, ricinoleic. acid, various mixed fatty acidsderived -from unsaturated oils, such as teaseed oil, sunflower seed oil,orthe like, and lauric acid,

in various examples appearing in the aforemen tioned patent to- Katzmanand Harris, No. 2,238,902. 7 i

In view of whathas been said, it is obvious that numerous 'hydroxylatedester diamides are If primary amines are reacted-with dibasic acids oresters, one may obtain diamides in which at least one amino hydrogenatom is replaced by a hydrocarbon radical containing, for example, 4-12carbon atoms. Such diamides are additionally characterized by thepresence of one or more amido hydrogen atoms. Such diamides areadditionally characterized by the presence of one or more amido hydrogenatoms. Such diamides can be. treated with ethylene oxide or the liketo'give hydroxylated derivatives. Similarly, one may react" diethyloxalate, diethyl phthalate, diethyl maleate, or the like, with ethylethanolamine. p fopyl ethanolamine', ethyl propanolamine,ethylglycerylamine, or the like.

-Wherever they use of anoxyalkylating agent is suggested, it isunderstood that glycid maybe mulas:

employed, as well as ethylene oxide, propylene oxide, or similarreactants. As illustrating such hydrcxylated ester diamides, referenceis made to the following for- OHR'COOCzlEh yNC-R-CN OHC2H4 OHRCOOCzHi OCHLOE O 0 I II In the above formulas, OC-RCO represents theacyl radicalderived from a dibasic acid having 10 carbon atoms or less. OH.R'COrepresents the acyl radical of a hydroxylated acid, such as ricinoleicacid, hydroxystearic acid, or similar acids obtained by oxidation, suchas blown oleic acid, or acids obtained by the hydrolysis of blown olein.Such acyl radicals all contain at least 8 and not more than 32 carbonatoms, and are apt to contain 18 carbon atoms. R"CO is the acyl radicalderived from a non-hydroxylated monocarboxy detergent-forming acid,particularly an unsaturated acid, such as oleic acid, linoleic acid,etc. It is understood, of course, Y. that a mixture of fatty acids maybe employed instead of a single fatty acid. R' is a hydrocarbon radicalhaving 4-12 carbon atoms.

In examining the above formulas, it is to be noted that the esterdiamides may be obtained from monobutanolamine, dibutanolamine,monopropanolamine, 'dipropanolamine, monoglycerylamine, diglycerylamine,or the like, instead of being derived from monoethanolamine ordiethanolamine. Similarly, th products shown in some of the formulas arederived from tris(hydroxymethyl) aminomethane. Similarly, derivativesmay be derived from 2-amino-2-ethyl-1,3-propane diol and 2-amino-2-methyl- 1,3 -propane diol.

It has been pointed out that the hydroxylated ester diamides may bederived in any suitable way, such as reaction with ammonia, followed byoxyethylation, or some other suitable procedure. Not only may thedibasic acids or their function.- al equivalents be reacted withammonia, but, as has been brieflysuggested previously, such acids may bereacted with a primary amine, such as any suitable alkylamine, or analieyclic amine;

or an arylamine, or an aralkylamine, to give the amide or substitutedamide, provided, of course, that such compound contains at least oneamino hydrogen atom. More speciflcally,\ suitable amines which may beemployed as reactants include butylamine, amylamine, octylamine,decylamine, cyclohexylamine, benzylamine, phenylamine, etc. Generallyspeaking, when an amine is employed instead of ammonia for reaction withthe low molal dibasic acid, one preferably employs a hydroxylateddetergent-forming acid. such as ricinoleic acid, in order to insure aplurality 01 available alcoholic hvdro'xyl groups, for subsequentreaction with the polybasic carboxy acid or with 2 pound moles ofdiethanolamine to give a vdiamide of the following formula:

'QHCaHa 0 0 0111.011 NtLiN oncim canon One pound mole of such diamide isreacted complete. as indicated by the substantial elimiits equivalent.This is understandable by considering reactions involving, for instance,one

mole of diethyl oxalate and one mole of dibutylamine and one mole ofbutylamine. The compound so obtained would consist of a proportion ofdiamides having no amino hydrogen atoms, a fraction containing one aminohydrogen atom, and a fraction containing two amino hydrogen atoms.Intermediate reactants so derived having one amino hydrogen atom, wouldbe substantially inert for reactions involving phthalicanhydride, unlessone femployed an ydroxylated polybasic acid, such as malic acid,tartaric acid, or vcitric acid. In such an event, if the intermediatereactant was subsequently reacted as an alcohol, a resinification wouldbe possible, especially provided that such intermediate ester had beentreated with glycid or the like, prior to reaction with phthalic acid.It will be noted in the previous formulas, however, that wherericinoleic acid is employed as the reactant to supply the high molalacyloxy radical, then the hydroxyl radical, which is part of thericinoleyl radi-' cal,'would serve as a reactive function forcombination with phthalic anhydride or the like by esterification. Qtherhigher fatty acids, such as hydroxystearic acid, aleuritic acid, etc.,may be employed. The fact that glycid or the like may be employed toreplace a labile atom or a hydroxyl radical by the equivalent of twohydroxyl radicals, is well known.

In any event, the reaction of the hydroxylated ester diamide of the kinddescribed with a polybasic carboxy acid or its functional equivalent.such as the anhydride, is.a well-known reaction and is nothing more orless than an esteriflcation reaction 0! the kind employed to producephthalated castor oil, phthalated ricinoleoarnide, etc. For instance,common comparable reactions are described in U. S. Patent No. 1,976,602,dated October 9, 1934, to De Groote, Keiser and Adams.

and U. S. PatentNo. 2,078,652, to De Groote and '"Keiser, dated .April2'7, 1937. Briefly stated, the

Example 1 phthalate.

nation of two alcoholic hydroxyl radicals. The product so obtained hastwo free hydroxyl radicals and two free carboxyl radicals.

Example 2 A product is prepared in the same manner as described in theprevious example, except that the diamide is derived from diethylphthalate.

Example 3 Aproduct is prepared in the same manner as described inExample 1, except that the diamide is derived from dlethyl maleate.

I Example 4 A product is prepared in the same manner as described in theprevious examples, except that one pound mole of ricinoleic acid isemployed instead of two pound moles of ricinoleic acid; and one poundmole of phthalic -anhydride is employed instead of two pound moles ofphthalic anhydride. Such compounds may be prepared from diethyl oxalate,diethyl maleate, or diethyi Esteriflcation is so controlled, that thefinal product has one free carboxyl radical.

Example 5 The'same procedure is followed as in Example d, preceding,except that the ester diamide is derived from monoethanolamine insteadof diethanolamine.

Example 6 Example 7 The same procedure is followed as in Example 1, 2,3, or 4, except that dibutanolamine or dipropanolamine is substitutedfor diethanolamine.

Example 8 'irismydroxymethyimminomethane is substituied fordiethanolamine in Examples 1, 2, 3, and 4. preceding.

Example 9 v The same procedure is followed as in the preceding examples,except that a non-'hydroxy acid, such as oleic acid, is substituted forricinoleic' acidin the various examples in which there is a residualhydroxyalkyl radical, as differentiated from the hydroxyaeyl radicalpresent in ricinoieic acid.

- Emmplelo Esteriflcation of hydroxylated ester diamide is accomplishedby means ot maleic an- .One pound mole of'diethyl oxalate is reactedhydrideeinstead of phthalic anhydride.

' Example 11 Esteriflcation is accomplished by means of succinic acid,instead of phthalic anhydride.

Example 12 Esteriflcation is accomplished by means of oxalic acidinstead of phthalic anhydride.

In such instances where oxalic acid is employed, it is desirable to usea lower temperature, in view of the fact that oxalic acid or most of its"functional equivalents, decompose at a temperaacid, such as benzenesulfonic acid. In other instances the reaction is most suitablyconducted in the presence of an inert high boiling solvent, such asxylene. The-xylene is continuously distilled under a reflux condenser;condensed by such condenser, and returned to the reaction chamberthrough a trap. The xylene vapors carry off the water, which-is removedafter being condensed by the trap. This is a conventional procedure,commonly employed in this type or similar types of reaction.

7 Although we prefer to use phthalic anhydride as the most desirablesource of the polybasic oarboxy acid, one may use other polybasiccarboxy acids or their anhydrides, such as succinic, malic,

fumaric, citric, maleic, adipic, tartaric, glutaric,

diphenic, naphthalic, oxalic, pimelic, suberic,

azelaic, sebacic, etc. Naturally, a simple derivative'fof a polybasicacid, such as chlorophthalic acid, can be used as advantageouslyasphthalic acid itself, although there is no added advantage in the use ofthe more costly chemical compounds.

In view of'the large number of reactants and types of materialsdescribed, it may be well to note those which we particularly prefer. Ithas been pointed out that we prefer to use unsaturated fatty acids asthe source of the high molal oxyacyl radical, and particularly, the hy--drgx'ylated fatty acid commonly available, to

witfrecinoleic acid. We prefer to use phthalic '-aci d,-maleic acid, ortheir anhydrides, or oxalic acid as the source of the polybasic carboxyacid,

. -.elther when employed to furnish the acyl radi- 1 cal,- i. e., theradical in which the carbonyl carb'o'n atom is directly linked to anamino nitrogen atom; or, when employed for esteriiication, where theacyloxy radical indicated thus:

- oo'o-it-coo is present. We prefer to use monoethanolamine or;diethanolamine its-the reactant for the formation of the substituteddiamide employed for subsequent reaction to produce the ester diamide.

In view of what has been said, it is apparent that hydroxylated esterdiamides of the kind described previously may be considered for the sakeof simplicity, as being in the class of an alcohol, .1. e., a monohydricor polyhydric alcohol.

"If F an alcohol' is indicated by the formula :Y'(OH);, where nindicates the number 1 or 76 more, and if a polybasic acid body beindicated by..the formula X'(COOH) a, where 1: indicates the number 2 ormore, then the reaction between a monohydric alcohol 'and a polybasicacid will result in a compound which may be indicated by the followingformula:

wherein 11. indicates the number 1 or more, .and which is 'in reality acontraction of a more elaborate structural formula, in which X and Y arejoined by a carboxyl radical or residue. Assuming, however, as would betrue in the ma-- jority of cases, that the alcohol actually would be apolyhydric alcohol, and that the acid body would be polybasic in nature,for instance, if one employed a diphthalate of a polyhydroxylated esterdiamide of the kind previously described, then examination reveals thatthe formulainight result in a combination, in which there were neitherresidual carboxyl radicals, nor residual hydroxyl radicals, or mightresult in compounds in which there were residual hydroxyl radicals, andno residual carboxyl radicals, or compounds where there might beresidual carboxyl radicals and no residual hydroxyl radicals; or theremight be both. This is indicated by the following:

in which q indicates a small whole number (one in the case of a monomer,and probably not over .20 andusually less than 10), and m andn' indicate the number 1 or more, and m" and n indicate zero or a small ormoderately-sized whole number, such as zero, one or more, but in -anyevent, probably a number not in excess of 10-15. Naturally, eachresidual 'hydroxyl could combine with a phthalic acid body or itsequivalent, or with a similar compound derived from a tribasic acid,such as citric acid; and in such event, there would be a large number offree or uncombined carboxyl radicals present, possibly 20 or more.Actually, the preferable type of reagent would be more apt to includeless than 20, and in fact, less than -10 free hydroxyl radicals. It isnot necessary to remark that the residual carboxyl radicals can bepermitted to remain as such, or can be neutralized in any suitablemanner, such as conversion into salts, esters, amides, amino esters, orany other suitable form. Usually, such conversion into salt form wouldbe by means of sodium hydroxide, potassium hydroxide, calcium hydroxide,magnesium hydroxide, ammonium hydroxide, amylamine, butanolamine,ethanolamine, diethanol a m i n e triethanolamine, cyclohexanolamine,benzylamine, aniline, toluidine, etc. Conversion into'the ester would beby means of a monohydrlc alcohol, such as methyl alcohol, ethyl alcohol,propyl alcohol, butyl alcohol, hexyl alcohol,

octyl alcohol, decyl alcohol, ethylene glycol, diethylene lycol,glycerol, diglycerol, triethylene glycol, or the like. One could employan amino alcohol so as to produce an ester.

We have found, however, as suggested, that the most suitable productsare sub-resinous, semi-resinous, or balsam-like products, and arepreferably derived from polyhydroxylated reactants, i. e.,polyhydro'xylated ester diamides. We have found that such products aresoluble to a fairly'definite extent; for instance, at least 5% in somesolvent, suchas water, alcohol, benzene,

be indicated by the following formula:

OH) m" in which the characters have their previous significance, and :11represents a small whole number not greater than 5, and 1: represents asmall whole number not greater than 5; Z represents a hydrogen ionequivalent, such as a metallic atom, organic radical, etc.

It may be well to emphasize that the intermediate products employed foresterification with phthalic anhydride or the like have also beenempioyed'as intermediates in the production of other compounds, forinstance, typical wetting agents, especially by reactions which involvethe introduction of sulfo groups, so as to produce surface-active,water-soluble sulfonic acids or salts thereof. Such salts are entirelydifferent from the sub-resinous materials herein contemplated, and whichare apt to be water-insoluble, and in fact, their preferred form, isinvariably waterinsoluble; but even if water-soluble, they are notwetting agents and do not possess the characteristic property of wettingagents, but only the property of a soluble resin. It is also to be notedthat the molecular size of the compounds herein contemplated is entirelydifierent from the simpier monomeric sulfo salts that serve as wettingagents. The preferred form of the present compounds, particularly foruse as demulsifiers, are the water-insoluble form, i. e., the form.which shows solubility in water to the extent or one part per thousand,or less, thus clearly diiferentiating' from ordinary water-solublecompounds, and yet not excluding water solubility within the ratio thatdemulsifiers may be used in th oil fields, for instance, one part per10,000, or one part per 20,000, or one part per 30,000, or in suchrange.

It will -be noted that compounds of the type just described having atleast one hydrophobe nucleus are designated as being polar when there ispresent either an unesterified hydroxyl radical, or an unesterifiedcarboxyl radical, or both. We have found that the polar type of materialis by far the most eilective for demulsification, and it is ourpreference to use such type. Indeed, this particular type is so muclrmore effective for demulsiilcation than the non-polar such as water; ptroleum hydrocarbons, such as gasoline, kerosene, stove oil: a coal tarproduct, such as benzenaioluene, xylene, tar acid oil, cresol, anthracmeoil, etc. Alcohols, particularly aliphatic alcohols, such as methylalcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl 75alcohol, hexyl alcohol, octyl alcohol, etc., may be employed asdiluents. Miscellaneous solvents, such as pine oil, carbontetrachloride, sulfur dioxide extract obtained in the refining ofpetroleum, etc., may be employed as diluents. Similarly, the material ormaterials employed as the demulsifying agent of our process may beadmixed with one or more ,of the solvents customarily used in connectionwith conventional demulsifying agents. Moreover, said material ormaterials may be used alone, or in admixture with other suitable wellknown classes of demulsifying agents.

It is well mown that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth 011 and water solubility Sometimes they.

may be used in a form which exhibits relatively limited oil solubility.However, since such re-.

solubility within the concentration employed.

This same fact is true in regard to the material or materials employedas the demulsifying agent of our process.

We desire to point out that the superiority of the reagent ordemulsifying agent contemplated in our process'is based upon its abilityto treat certain emulsions more advantageously and at a, somewhat lowercost than is possible with other available demulsifiers, or conventionalmixtures thereof. It is believed that the particular demulsifying agentor treating agent herein described will find comparatively limitedapplication, so far as the majority of oil field emulsions areconcerned; but we have found that such a demulsitying agent hascommercial value, as it will economically break or resolve oil fieldemulsions in a number of cases which cannot be. treated as easily or atso low a. cost with the demulsifying agents heretofore available.

In practising our process for resolving petro- I combination with otherdemulsifying procedure,

such as the electrical dehydration process.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

' 1. A process for breaking petroleum emulsions of the water-in-oiltype, which consists in subjecting the emulsion to the action of ademulsifier, comprising a sub-resinous esterlfication product of thefollowing formula type:

coon).

cooz

in which 1: and y are small whole numbers not greater than 10 and m, n,and m are small whole numbers not over 10, and including zero; Z is anacidic hydrogen atom equivalent: and X is a residue derived from apolybasic carboxy acid; and .Y is a residue derived from a hydroxylatedester diamide, containing (a) an acyl radical derived from a polybasiccarboxy acid having not over 10 carbon atoms and amido-linked to bothamino nitrogen atoms;. and (b) at least C O OH) I in which a:' and 11'are small whole numbers not greater than 10 and m n, and m are smallwhole numbers not over 10, and including zero; Z is an acidic hydrogenatom equivalent; and x is a residue derived from a polybasic carboxyacid; and Y is a resdue derived from a .hydroxylated ester diamide,containing (a) an acyl radical derived from a polybasic carboxy acidhaving not over 10 carbon atoms and amido-linked to both amino nitrogenatoms; and (b) at least one acyloxy radical derived from a monocarboxydetergent-forming acid having at least 8 and not more than 32 carbonatoms, and linked by a divalent aliphatic radical to an amino nitrogenatom.

3. A processfor breaking petroleum emulsions of the water-in-oil type,which consists in subjecting the emulsion to the action of ademulslfier, comprising a substantially water-insoluble, sub-resinous,polar esteriflcation product of the following formula type:

coon)- oH).(Y,"x.')

in which a," and y are small whole numbers not greater than 10 and m, n,and m are small whole numbers not over 10, and including zero; Z is anacidic hydrogen atom equivalent; and x is a residue derived from apolybasic carboxy acid; and Y is a residue derived from a hydroxylatedester diamide, containing (a) an acyl radical derived from a polybasiccar-boxy acid having not over 10 carbon atoms and amide-linked to bothamino nitrogen atoms; and (b) at le st one acyloxy radical derived froma mono arboxy detergent-forming acid having at least 8 and not more than32 carbon atoms, and linked by a divalent aliphatic radical to an aminonitrogen atom.

4. A process for breaking petroleum emulsions of the water-in-oil type,which consists in subjecting the emulsion to the action of ademulsifier, comprising a substantially water-insoluble, sub-resinous,polar esterification product of the following formula type: I

' coon). v

' (0H)(Yy'X;')

000.2)... in which m and y are small whole numbers not greater than 10and m n, and m are small whole numbers not over 10; and including zero;Z is an acidic hydrogen atom equivalent; and X is I a residue derivedfrom a dibasiccarboxy acid; and Y is a residue derived from ahydroxylated ester diamide, containing (a) an acyl radical derived froma dibasic carboxy acid having not over 10 carbon atoms and amido-linkedto both amino nitrogen atoms; and (b) at least one acyloxy radicalderived from a monocarboxy detergent-forming acid having at least 8 andnot more than 32 carbon atoms, and linked by a divalent aliphaticradical to an amino nitrogen.

5. A process for breaking petroleum emulsions of the water-in-oil type,which consists in subjecting the emulsion to the action of ademulsifler, comprisinga substantially water-insoluble, sub-resinous,polar esteriflcation product of the following formula type:

coon)... H)-( in which a:' and u are small whole numbers not greaterthan 10 and m, n, and m are small whole numbers not over 10, andincluding zero; Z is an acidic hydrogen atom equivalent; and X is aresidue derived from a di-basic carboxy acid;

and Y is a residue derived from a hydroxylated ester diamide, containing(a) an acyl radical derived from a dibasic carboxy acid having not over10 carbon atoms and amide-linked to both amino nitrogen atoms; and (b)at least one acyloxy radical derived from a fatty acid having at least 8and not more than 32 carbon atoms.

and linked by a divalent aliphatic radical to an amino nitrogen atom. V

6. -A process for breaking petroleum emulsions of the water-in-oil type,whichconsists in subjecting the' emulsion to the action of a demulsi-vfier, comprising a substantially water-insoluble, sub-resinous, polaresterification product of the following formula type:

coon

in which :12 and i! are small whole numbers not greater than 10 and m,n, and m are small whole numbers not over 10, and including zero; Z isan acidic hydrogen atom equivalent; and X is a Y is a residue derivedfrom a hydroxylated ester diamide,-containing (a) an acyl radicalderived, from a dibasic carboxy acid having not over 19 carbon atoms andamide-linked to both amino nitrogenatoms; and (b) at least one acyloxyradiin which a:' and 11' are small whole number not greater than 10 andm, n, and m are small whole numbers not over 10, and including zero;'Zis an acidic hydrogen atom equivalent; and X is a residue derived from adibasic carboxy acid; and Y is a residue derived from a hydroxylatedester diamide, containing (a) an acyl radical derived from a dibasiccarboxy acid havingnot over 10 carbon atoms and amido-linked to bothamino nitrogen atoms; and (b) at least one ricinoleyl residue derivedfrom a dibasic carboxy acid; and

7. A process for breaking petroleum emulsions oxy radical, linked by adivalent aliphatic radical to an amino nitrogen atom.

8. A process for breaking petroleum emulsions of the water-in-oii type,which consists in subjectins the emulsion to the action of ademulsifier,

comprising a substantially water-insoluble, subnitrogen atoms; and (b)at least one ricinoleyl oxy radical, linked by a divalent aliphaticradical to an amino nitrogen atom.

9. A process for breaking petroleum emulsions oi the water-in-oil type.which consists in subiecting the emulsion to the action of ademulsifier, comprising. a substantially water-insoluble, subresinous,polar esteriflcation product of the following formula type:

coon

( hWa' -I') 000.2) :a' in which a and y are small whole numbers notgreater than 10 and m, n, and m are small whole numbers not over 10, andincluding zero; Z is an acidic hydrogen atom equivalent; and X is aresidue derived from a dibasic carboxy acid; and 5 Y is a residuederived fromha hydroxylated ester diamide, containing (a) an acylradical derived from oxalic acid and amido-linked to both amino nitrogenatoms; and (b) at least one ricinoleyl oxy radical, linked by a divalentaliphatic radical to an amino nitrogen atom.

10. A process for breaking petroleum emulsions of the water-in-oil type,which consists in subiecting the emulsion to the action of ademulsifier,

comprising a substantially water-insoluble, subresinous, polaresterification product of the following formula type:

( HM-W lie) 000.2 I in which as and 21' are small whole numbers notgreater than 10 and m, n, and m are small whole numbers not over 10, andincluding zero; Z is an acidic hydrogen atom equivalent; and X is aresidue derived from a dibasic carboxy acid; and Y is a residue derivedfrom a hydroxylated ester diamide, containing (a) an acylradicalderived' from maleic acid and amido-linked to both amino nitrogenatoms; and (b) at least one ricinoleyl oxy radical, linked by a divalentaliphatic radical to an amino nitrogen atom.

mnvm DE GROO'I'E. BERNHARD mean.

